CN117088920B - Pt complex and application thereof in organic light-emitting device - Google Patents

Pt complex and application thereof in organic light-emitting device Download PDF

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CN117088920B
CN117088920B CN202311356945.2A CN202311356945A CN117088920B CN 117088920 B CN117088920 B CN 117088920B CN 202311356945 A CN202311356945 A CN 202311356945A CN 117088920 B CN117088920 B CN 117088920B
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complex
compound
deuterium
hydrogen
organic
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CN117088920A (en
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赵晓宇
张磊
申屠晓波
刘运起
吴空物
孔祥贞
叶绪兵
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Zhejiang Huadisplay Optoelectronics Co Ltd
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Zhejiang Huadisplay Optoelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to the technical field of organic photoelectric material preparation, in particular to a Pt complex and application thereof in an organic light-emitting device. The Pt complex provided by the invention has very low efficiency roll-off, by introducing the triphenylsilicon large steric hindrance group, the close packing among planar Pt complex molecules is effectively reduced, the luminescence quenching effect caused by the interaction among luminescent molecules is inhibited, the energy transmission between a host material and a guest material is effectively improved, and the device efficiency is further improved. So that the Pt complex has a very low roll-off efficiency. The Pt complex is used as a functional layer, particularly used as a light-emitting layer to manufacture an organic electroluminescent device, the current efficiency is improved, the lighting voltage is reduced, the service life of the device is greatly prolonged, and the energy is effectively transferred to the Pt complex for light emission instead of heat after most electrons and holes are combined.

Description

Pt complex and application thereof in organic light-emitting device
Technical Field
The invention relates to the technical field of organic photoelectric material preparation, in particular to a Pt complex and application thereof in an organic light-emitting device.
Background
With the development of multimedia technology and the improvement of informatization requirements, the requirements on the performance of panel displays are higher and higher. The OLED has a series of advantages of autonomous luminescence, low-voltage direct current drive, full solidification, wide viewing angle, rich colors and the like, and is widely paid attention to potential application in a new-generation display and illumination technology, so that the OLED has a very wide application prospect. The organic electroluminescent device is a spontaneous luminescent device, and the mechanism of OLED luminescence is that electrons and holes are respectively injected from positive and negative poles and then migrate, recombine and decay in an organic material under the action of an external electric field to generate luminescence. Typical structures of OLEDs include one or more functional layers of a cathode layer, an anode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, a hole injection layer, and a light emitting layer. Although the research progress of organic electroluminescence is very rapid, there are still many problems to be solved, and the green Pt complex with high efficiency and long lifetime has been a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a Pt complex and application thereof in an organic light-emitting device. By introducing the triphenylsilicon large steric hindrance group, the close packing between planar Pt complex molecules is effectively reduced, the luminescence quenching effect caused by interaction between luminescent molecules is inhibited, the energy transmission between a host material and a guest material is effectively improved, and the concentration of high-energy excitons in a luminescent layer is reduced, so that the green light material with high efficiency and long service life is realized. Such Pt complexes therefore find important application in organic light emitting devices.
In order to achieve the purpose of the invention, the technical scheme of the invention is as follows:
according to one or more embodiments, the present invention provides a Pt complex having a structure represented by formula I:
in the formula I, the ring A is selected from five-membered ring, five-membered heterocycle, six-membered ring or condensed ring, wherein hetero atom is nitrogen atom, oxygen atom or sulfur atom;
said R is 1 、R 2 、R 3 、R 4 Each independently of the others is a single substituent up to the maximum number of substitutions possibleA group or no substituent, any adjacent substituents optionally joined or fused to form a ring; r is R 1 、R 2 、R 3 、R 4 Each independently selected from the group consisting of hydrogen (H), deuterium (D), C1-C24 alkyl, C1-C24 deuterated alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 aza-aryl, C6-C30 aryl-silane, and; r is R 4 Can form a condensed ring with the ring A where the condensed ring is positioned by sharing the ring edge.
In some embodiments of the compounds, in formula I, the R 1 Selected from C1-C10 alkyl, C3-C10 cycloalkyl, R 2 、R 3 、R 4 Each independently selected from the group consisting of hydrogen, deuterium, C1-C10 alkyl, C1-C10 deuterated alkyl, C3-C10 cycloalkyl, C6-C18 aryl, and combinations thereof.
R 4 Selected from the group consisting of hydrogen, deuterium, C1-C10 alkyl, C1-C10 deuterated alkyl, C3-C10 cycloalkyl, C6-C18 aryl, C6-C18 aza-aryl, C18-C30 aryl silane, and combinations thereof.
In some embodiments of the compounds, ring a in formula I is selected from furyl, thienyl, benzofuryl, benzothienyl, phenyl ring, fluorenyl, N-heterofluorenyl, spirofluorenyl.
In some embodiments of the compounds, R in formula I 1 Selected from hydrogen, deuterium, t-butyl or amantadine.
R 2 Selected from the group consisting of hydrogen, deuterium, t-butyl, amantadine, phenyl, biphenyl, and combinations thereof.
R 3 Selected from the group consisting of hydrogen, deuterium, t-butyl, phenyl, biphenyl, and combinations thereof.
R 4 Selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, butyl, t-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, amantadine, phenyl, biphenyl, fluorenyl, N-heterofluorenyl, pyridinyl, triarylsilane, and combinations thereof.
As a preference, R in formula I 1 -R 4 The hydrogen atoms in the radicals may be partially deuterated or fully deuterated, R in formula I 1 -R 4 ArbitraryAdjacent two substituents are not linked or are linked to each other to form a ring structure.
According to one or more embodiments, the Pt complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:
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in another aspect, the invention also provides application of the Pt complex with the general structure shown in the formula I in preparation of an electronic device.
Further, the electronic device includes an organic photovoltaic device, an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field quench device (O-FQD), a light emitting electrochemical cell (LEC), and an organic laser diode (O-laser).
Alternatively, pt complexes of the general structure shown in formula I above are used as light emitting layer materials for electronic devices.
In another aspect, the present invention also provides an organic electroluminescent device comprising a cathode, an anode, and at least one organic functional layer therebetween; the organic functional layer comprises a Pt complex with a general structure shown in the formula I.
Further, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a Pt complex with a general structure shown in the formula I. The mass percentage of the Pt complex is 0.1% -50%.
In another aspect, the invention also provides an organic photoelectric device, a substrate layer and a first electrode; a second electrode facing the first electrode; and a luminescent material layer disposed between the first electrode and the second electrode; wherein the luminescent material layer comprises Pt complex with the general structure shown in the formula I. For example, the Pt complex may be included as a dopant in the light emitting material layer.
The invention also provides a composition, which comprises the Pt complex with the general structure shown in the formula I.
The invention also provides a preparation comprising the Pt complex with the general structure shown in the formula I or the composition and at least one solvent. The solvent is not particularly limited, and for example, an unsaturated hydrocarbon solvent such as toluene, xylene, mesitylene, tetrahydronaphthalene, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, a halogenated saturated hydrocarbon solvent such as carbon tetrachloride, chloroform, methylene chloride, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, a halogenated unsaturated hydrocarbon solvent such as chlorobenzene, dichlorobenzene, trichlorobenzene, an ether solvent such as tetrahydrofuran, tetrahydropyran, an ester solvent such as an alkyl benzoate, and the like, which are known to those skilled in the art, can be used.
The invention also provides a display or lighting device comprising one or more of the organic electroluminescent devices as described above.
Compared with the prior art, the invention has the beneficial effects that:
the Pt complex provided by the invention has very low efficiency roll-off, by introducing the triphenylsilicon large steric hindrance group, the close packing among planar Pt complex molecules is effectively reduced, the luminescence quenching effect caused by the interaction among luminescent molecules is inhibited, the energy transmission between a host material and a guest material is effectively improved, and the device efficiency is further improved. So that the Pt complex has a very low roll-off efficiency. The Pt complex is used as a functional layer, particularly used as a light-emitting layer to manufacture an organic electroluminescent device, the current efficiency is improved, the lighting voltage is reduced, the service life of the device is greatly prolonged, and the energy is effectively transferred to the Pt complex for light emission instead of heat after most electrons and holes are combined.
Detailed Description
The following describes the present invention in detail. The following description of the constituent elements may be based on the representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. The present disclosure may be understood more readily by reference to the following detailed description and the examples included therein. Before the present compounds, devices and/or methods are disclosed and described, it is to be understood that, unless otherwise indicated, they are not limited to specific synthetic methods or specific reagents as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, the exemplary methods and materials are now described.
"C1-C24 alkyl" as used herein refers to monovalent alkyl groups having 1 to 24 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of this term are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl and the like.
"cycloalkyl" as used herein for C3-C24 refers to a cyclic alkyl group having 3 to 14 carbon atoms and having a single or multiple ring fused, optionally substituted with 1 to 3 alkyl groups. Such cycloalkyl groups include, for example, a single ring structure such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, 1-methylcyclopropyl, and 2-methylcyclopentyl, 2-methylcyclooctyl, etc., or a multiple ring structure such as adamantyl, etc.
As used herein, "C6-C30 aryl" refers to an unsaturated aromatic carbocyclic ring having 6 to 30 carbon atoms and having a single ring (e.g., phenyl) or a multiple ring fused (e.g., naphthyl or anthracenyl). Preferred aryl groups include phenyl, naphthyl, and the like. Unless otherwise defined for the individual substituents, such aryl groups may be optionally substituted with 1 to 3 of the following substituents: hydroxy, acyl, acyloxy, alkyl, alkoxy, alkenyl, alkynyl, amino, aminoacyl, aryl, aryloxy, carboxyl ester, aminocarboxyl ester, cyano, halogen, nitro, heteroaryl, heterocycle, thioalkoxy, trihalomethyl, and the like. Preferred substituents include alkyl, alkoxy, halogen, cyano, nitro, trihalomethyl and thioalkoxy. But is not limited thereto.
The "heterocycle" as used herein refers to a generic term for groups in which one or more carbons in the ring are replaced by heteroatoms including, but not limited to, oxygen, sulfur or nitrogen atoms, and the heterocycle may be a monocyclic heterocarbyl, monocyclic heteroaryl, fused heterocarbyl or fused heterocarbyl, examples of which may include, but are not limited to, pyridyl, pyrrolyl, pyridyl, thienyl, furyl, indolyl, quinolinyl, isoquinolinyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and the like.
As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes a mixture of two or more components.
Unless otherwise indicated, all commercial reagents referred to in the following experiments were used directly after purchase.
In a preferred embodiment of the present invention, the OLED device of the present invention comprises a hole transporting layer, and the hole transporting material may preferably be selected from known or unknown materials, particularly preferably from the following structures, but does not represent that the present invention is limited to the following structures (Ph is phenyl):
in a preferred embodiment of the present invention, the hole injection layer is comprised in the OLED device of the present invention. The preferred hole injection layer materials of the present invention are of the following structure, but do not represent the invention as limited to the following structure:
in a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the following compounds, but does not represent the present invention limited to the following structures:
the OLED device of the present invention contains a host material, which may be selected from known or unknown materials, particularly preferably selected from the following structures, but does not represent the limitation of the present invention to the following structures:
the preparation method of the Pt complex, i.e., the guest compound, and the light emitting performance of the device are explained in detail in connection with the following examples.
EXAMPLE 1 Synthesis of Compound 1
Synthesis of Compounds 1-3: compound 1-1 (290 mg,1 mmoL) and compound 1-2 (178 mg,1 mmoL) were dissolved in 50 mL toluene solution. 10 mL aqueous sodium carbonate (2M) and tetrakis (triphenylphosphine) palladium (57 mg,0.05 mmoL) were added under nitrogen. After the reaction system was refluxed for 48 hours, it was cooled to room temperature. The solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent is removed by reduced pressure distillation, the crude product is separated and purified by a silica gel chromatographic column, and the leaching agent is as follows: dichloromethane: petroleum ether = 1:1, to give product 1-3 (150 mg, yield 43%). Mass spectrum m/z, theory 345.11; actual measurement value M+H:346.14.
synthesis of Compounds 1-5: compounds 1-3 (345 mg,1 mmoL) and compounds 1-4 (205 mg,1 mmoL) were dissolved in 50 mL anhydrous toluene solution. Sodium tert-butoxide (192 mg,2 mmoL), palladium acetate (12 mg,0.05 mmoL) and tri-tert-butylphosphine tetrafluoroborate (145 mg,0.5 mmoL) were added under nitrogen atmosphere. The reaction system was refluxed for 72 hours and then cooled to room temperature. The solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent is removed by reduced pressure distillation, the crude product is separated and purified by a silica gel chromatographic column, and the leaching agent is as follows: dichloromethane: petroleum ether = 1:1, product 1-5 (212 mg, 45% yield) was obtained. Mass spectrum m/z, theory 470.37; actual measurement value M+H:471.39.
synthesis of Compounds 1-7: compounds 1 to 5 (470 mg,1 mmoL) and compounds 1 to 6 (283 mg,1 mmoL) were dissolved in 50 mL anhydrous toluene solution. Sodium tert-butoxide (192 mg,2 mmoL), palladium acetate (12 mg,0.05 mmoL) and tri-tert-butylphosphine tetrafluoroborate (145 mg,0.5 mmoL) were added under nitrogen atmosphere. The reaction system was refluxed for 72 hours and then cooled to room temperature. The solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent is removed by reduced pressure distillation, the crude product is separated and purified by a silica gel chromatographic column, and the leaching agent is as follows: dichloromethane: petroleum ether = 2:1, to give product 1-7 (230 mg, yield 37%). Mass spectrum m/z, theory 625.30; actual measurement value M+H:626.32.
synthesis of Compounds 1-8: buLi (0.5 mL,1 mmoL,2M in hexane) was slowly added to a solution of compounds 1-7 (625 mg,1 mmoL) in tetrahydrofuran (50 mL) at-78deg.C. After 3 hours of reaction, trimethyltin chloride (1 mL,1 mmoL,1M in Hexane) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, then allowed to react at 80℃for 6 hours. After cooling to room temperature, ice water 1 mL was added. The solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the crude product obtained was directly used for the next reaction.
Synthesis of Compounds 1-10: compounds 1 to 8 (711 mg,1 mmoL) and compounds 1 to 9 (282 mg,1 mmoL) were dissolved in 50 mL toluene solution. Tetrakis (triphenylphosphine) palladium (57 mg,0.05 mmoL) was added under nitrogen. After the reaction system was refluxed for 48 hours, it was cooled to room temperature. The solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent is removed by reduced pressure distillation, the crude product is separated and purified by a silica gel chromatographic column, and the leaching agent is as follows: dichloromethane: petroleum ether = 1:1, to give the product 1-10 (450 mg, yield 64%). Mass spectrum m/z, theory 701.33; actual measurement value M+H:702.35.
synthesis of Compounds 1-11: buLi (0.5 mL,1 mmoL,2M in hexane) was slowly added to a solution of compounds 1-10 (701 mg,1 mmoL) in tetrahydrofuran (50 mL) at-78deg.C. After 3 hours of reaction, triphenylchlorosilane (294 mg,1 mmoL) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, then allowed to react at 80℃for 6 hours. After cooling to room temperature, ice water 1 mL was added. The solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent is removed by reduced pressure distillation, the crude product is separated and purified by a silica gel chromatographic column, and the leaching agent is as follows: dichloromethane: petroleum ether = 1:2, to give the product 1-11 (467 mg, yield 53%). Mass spectrum m/z, theory 881.51; actual measurement value M+H:882.53.
synthesis of Compound 1: compounds 1-11 (882 mg,1 mmoL) and the compound bis (benzonitrile) platinum (II) (472 mg,1 mmoL) were dissolved in 50 mL benzonitrile solution. Under the condition of nitrogen atmosphere, the temperature is raised to 180 ℃ for reaction for 48 hours. After cooling to room temperature, the solvent was removed by rotary evaporation and the residue was extracted with dichloromethane (3×100 mL). The organic phase is washed with water and dried over sodium sulfate. The solvent is removed by reduced pressure distillation, the crude product is separated and purified by a silica gel chromatographic column, and the leaching agent is as follows: dichloromethane: petroleum ether = 1:2 to give product 1 (230 mg, yield 21%). Mass spectrum m/z, theory 1074.46; actual measurement value M+H:1075.48.
example 2: synthesis of Compound 6
Compound 6 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 26%. Mass spectrum m/z, theory 1286.62; actual measurement value M+H:1287.64.
example 3: synthesis of Compound 9
Compound 9 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 23%. Mass spectrum m/z, theory 1246.49; actual measurement value M+H:1247.51.
example 4: synthesis of Compound 12
Compound 12 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 22%. Mass spectrum m/z, theory 1202.43; actual measurement value M+H:1203.45.
example 5: synthesis of Compound 15
Referring to the synthetic route for compound 1, compound 15 was synthesized. The yield of the final product was 27%. Mass spectrum m/z, theory 1104.41; actual measurement value M+H:1105.43.
example 6: synthesis of Compound 21
Compound 21 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 24%. Mass spectrum m/z, theory 1194.46; actual measurement value M+H:1195.48.
example 7: synthesis of Compound 22
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Compound 22 was synthesized by reference to the synthetic route of compound 1. The yield of the final product was 21%. Mass spectrum m/z, theory 1236.51; actual measurement value M+H:1237.53.
example 8: synthesis of Compound 24
Compound 24 was synthesized referring to the synthetic route for compound 1. The yield of the final product was 31%. Mass spectrum m/z, theory 1210.49; actual measurement value M+H:1211.52.
example 9: synthesis of Compound 36
Referring to the synthetic route for compound 1, compound 36 was synthesized. The yield of the final product was 27%. Mass spectrum m/z, theory 1239.43; actual measurement value M+H:1240.45.
example 10: synthesis of Compound 44
Compound 44 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 25%. Mass spectrum m/z, theory 1206.55; actual measurement value M+H:1207.57.
example 11: synthesis of Compound 45
Compound 45 was synthesized referring to the synthetic route for compound 1. The yield of the final product was 24%. Mass spectrum m/z, theory 1246.49; actual measurement value M+H:1247.52.
example 12: synthesis of Compound 48
Compound 48 was synthesized referring to the synthetic route for compound 1. The yield of the final product was 26%. Mass spectrum m/z, theory 1202.43; actual measurement value M+H:1203.45.
example 13: synthesis of Compound 53
Compound 53 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 29%. Mass spectrum m/z, theory 1210.49; actual measurement value M+H:1211.52.
example 14: synthesis of Compound 61
Compound 61 was synthesized referring to the synthetic route for compound 1. The yield of the final product was 23%. Mass spectrum m/z, theory 1166.43; actual measurement value M+H:1167.45.
example 15: synthesis of Compound 65
Compound 65 was synthesized referring to the synthetic route for compound 1. The yield of the final product was 22%. Mass spectrum m/z, theory 1200.41; actual measurement value M+H:1201.43.
example 16: synthesis of Compound 74
Compound 74 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 26%. Mass spectrum m/z, theory 1230.46; actual measurement value M+H:1231.48.
example 17: synthesis of Compound 78
Referring to the synthetic route for compound 1, compound 78 was synthesized. The yield of the final product was 35%. Mass spectrum m/z, theory 1230.46; actual measurement value M+H:1231.48.
example 18: synthesis of Compound 79
Referring to the synthetic route for compound 1, compound 79 was synthesized. The yield of the final product was 32%. Mass spectrum m/z, theory 1256.48; actual measurement value M+H:1257.51.
example 19: synthesis of Compound 81
Referring to the synthetic route for compound 1, compound 81 was synthesized. The yield of the final product was 25%. Mass spectrum m/z, theory 1160.48; actual measurement value M+H:1161.51.
example 20: synthesis of Compound 84
Referring to the synthetic route for compound 1, compound 84 was synthesized. The yield of the final product was 21%. Mass spectrum m/z, theory 1160.48; actual measurement value M+H:1161.50.
example 21: synthesis of Compound 85
Referring to the synthetic route for compound 1, compound 85 was synthesized. The yield of the final product was 30%. Mass spectrum m/z, theory 1226.43; actual measurement value M+H:1227.45.
example 22: synthesis of Compound 89
Referring to the synthetic route for compound 1, compound 89 was synthesized. The yield of the final product was 31%. Mass spectrum m/z, theory 1210.45; actual measurement value M+H:1211.47.
example 23: synthesis of Compound 92
Compound 92 was synthesized by reference to the synthetic route of compound 1. The yield of the final product was 27%. Mass spectrum m/z, theory 1206.37; actual measurement value M+H:1207.39.
example 24: synthesis of Compound 96
Referring to the synthetic route for compound 1, compound 96 was synthesized. The yield of the final product was 23%. Mass spectrum m/z, theory 1190.39; actual measurement value M+H:1191.41.
example 25: synthesis of Compound 97
Compound 97 was synthesized referring to the synthetic route for compound 1. The yield of the final product was 28%. Mass spectrum m/z, theory 1188.50; actual measurement value M+H:1189.52.
example 26: synthesis of Compound 99
Referring to the synthetic route for compound 1, compound 99 was synthesized. The yield of the final product was 23%. Mass spectrum m/z, theory 1246.49; actual measurement value M+H:1247.51.
example 27: synthesis of Compound 105
Compound 105 was synthesized referring to the synthetic route of compound 1. The yield of the final product was 22%. Mass spectrum m/z, theory 1208.46; actual measurement value M+H:1209.48.
example 28: synthesis of Compound 110
Referring to the synthetic route for compound 1, compound 110 was synthesized. The yield of the final product was 28%. Mass spectrum m/z, theory 1218.40; actual measurement value M+H:1219.42.
example 29: synthesis of Compound 114
Compound 114 was synthesized with reference to the synthetic route of compound 1. The yield of the final product was 24%. Mass spectrum m/z, theory 1211.49; actual measurement value M+H:1212.51.
example 30: synthesis of Compound 118
Compound 118 was synthesized by reference to the synthetic route of compound 1. The yield of the final product was 24%. Mass spectrum m/z, theory 1257.47; actual measurement value M+H:1258.49.
example 31: synthesis of Compound 133
Referring to the synthetic route for compound 1, compound 133 was synthesized. The yield of the final product was 29%. Mass spectrum m/z, theory 1122.44; actual measurement value M+H:1123.46.
example 32: synthesis of Compound 137
Referring to the synthetic route for compound 1, compound 137 was synthesized. The yield of the final product was 26%. Mass spectrum m/z, theory 1208.47; actual measurement value M+H:1209.49.
manufacturing of OLED device:
as a reference preparation mode of an embodiment of a device, the invention comprises evaporating p-doped material on the surface or anode of ITO glass with the size of 2 mm multiplied by 2 mm of light-emitting area, or co-evaporating the p-doped material with a hole-transporting material at a concentration of 1% -50% to form a Hole Injection Layer (HIL) of 5-100 nm, forming a hole-transporting layer (HTL) of 5-200 nm on the hole injection layer, then co-evaporating a host material and a Pt complex (guest material) prepared by the invention at a volume ratio of 97:3 to form a light-emitting layer (EML) of 10-100nm, finally co-evaporating to form an electron-transporting layer (ETL) of 35 nm, and evaporating a cathode Al 70 nm, thereby manufacturing the organic electroluminescent diode.
In a preferred embodiment, the structure of the bottom-emitting OLED device provided by the present invention is: the glass containing ITO is used as an anode, and HIL is HT-1:P-3 (95:5, v/v%) and the thickness is 10 nanometers; HTL is HT-1 and has a thickness of 90 nanometers; EBL is HT-8, the thickness is 10 nanometers, EML is host material (H-9): compound 1 (97:3, v/v%) provided by the invention, the thickness is 35 nanometers, ETL is ET-3: liQ (50:50, v/v%) was 35 nm thick, and then an organic electroluminescent diode was prepared by evaporating 70 nm of cathode Al, which was designated as application example 1.
Referring to the method provided in application example 1, the prepared compound 6, compound 9, compound 12, compound 15, compound 21, compound 22, compound 24, compound 36, compound 44, compound 45, compound 48, compound 53, compound 61, compound 65, compound 74, compound 78, compound 79, compound 81, compound 84, compound 85, compound 89, compound 92, compound 96, compound 97, compound 99, compound 105, compound 110, compound 114, compound 118, compound 133 and compound 137 were used as the implementation object to replace compound 1, and a light-emitting layer was formed by co-evaporation with a host material compound at a volume ratio of 3:97, which was denoted as application examples 2 to 32.
Production of comparative example 1
Comparative example 1 was prepared with reference to the method provided in application example 1 described above, except that Pt-1 was used as the guest material of the light emitting layer in comparative example 1 instead of the Pt complex of the present invention. The chemical structure of compound Pt-1 in the comparative example is as follows:
the characteristics of the device examples and comparative examples prepared above, such as current efficiency, voltage and lifetime, were tested by standard methods, and the device luminescence characteristic data are shown in table 1.
TABLE 1 light emission characteristics data sheet for devices
As can be seen from table 1, compared with comparative example 1, application examples 1 to 32 exhibited good device performance in terms of both current efficiency and lifetime, and the improvement in the performance of each device application example was based on the Pt complex material of the present invention having a better ability to suppress the interaction between light-emitting molecules, and further, the Pt complex material was used as a host material for a light-emitting layer to prepare an electronic device having higher current efficiency and lifetime while reducing the driving voltage. The Pt complex provided by the invention has certain commercial application value.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (10)

1. A Pt complex, characterized in that the Pt complex has a structure represented by the following formula I:
in the formula I, the ring A is selected from benzofuranyl, benzothienyl, benzene ring, fluorenyl, N-heterofluorenyl and spirofluorenyl; the R is 1 、R 2 、R 3 、R 4 Each independently is a single substituent to the maximum number of substituents possible or no substituents, R 1 Selected from hydrogen, deuterium, C1-C10 alkyl, C3-C10 cycloalkyl; r is R 2 、R 3 Each independently selected from hydrogen, deuterium, C1-C10 alkyl, C1-C10 deuterated alkyl, C3-C10 cycloalkyl, C6-C18 aryl; the R is 4 Selected from hydrogen, deuterium, C1-C10 alkyl, C1-C10 deuterated alkyl, C3-C10 cycloalkyl, C6-C18 aryl, C6-C18 aza-aryl, C18-C30 aryl silane.
2. The Pt complex of claim 1, wherein R in formula I 1 Selected from hydrogen, deuterium, tert-butyl or adamantyl; r is R 2 Selected from hydrogen, deuterium, tertiary butyl, adamantyl, phenyl, biphenyl; r is R 3 Selected from hydrogen, deuterium, tert-butyl, phenyl, biphenyl.
3. The Pt complex of claim 1, wherein R 4 Selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, fluorenyl, N-heterofluorenyl, pyridinyl.
4. A Pt complex, characterized in that the Pt complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:
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5. use of a Pt complex according to any one of claims 1-4 in the manufacture of an electronic device.
6. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises a cathode, an anode and at least one organic functional layer interposed therebetween; the Pt complex according to any one of claims 1 to 4 is contained in the organic functional layer.
7. An organic optoelectronic device, comprising: a substrate layer, a first electrode; a second electrode facing the first electrode; and a luminescent material layer disposed between the first electrode and the second electrode; wherein the luminescent material layer comprises the Pt complex according to any one of claims 1 to 4.
8. A composition comprising the Pt complex of any one of claims 1-4.
9. A formulation comprising the Pt complex of any one of claims 1-4 and at least one solvent.
10. A display or lighting device comprising one or more of the organic electroluminescent devices of claim 6.
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